Liquid bleach-containing formulation for washing or cleaning

ABSTRACT

A substantially non-aqueous, free-flowing, storable liquid washing or cleaning formulation comprising: 
     A) from more than 20 to less than 78% by weight of at least one nonionic surfactant; 
     B) from 0.1 to 25% by weight of at least one anionic surfactant; 
     C) from 1 to less than 20% by weight of at least one water-soluble builder; and 
     D) from more than 20 to 35% by weight of at least one bleaching agent.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a non-aqueous bleach-containing formulationfor washing or cleaning which, besides the bleaching agent, containsnonionic and anionic surfactants and also builders and to a process forthe production of this formulation.

2. Statement of Related Art

Water-based washing and cleaning formulations generally contain anionicand nonionic surfactants. However, it has been found to be extremelydifficult to incorporate bleaching systems in such formulations. Inpractice, therefore, bleaching systems are often not used informulations of the type in question which results in a reduction intheir washing performance against bleachable soils. Some liquiddetergents available on the market contain very special bleachingsystems which, unfortunately, either have very low oxidation potentialsor are unstable and decompose even after only brief storage so thatthere is no improvement in washing activity against bleachable soils.

Various liquid detergent compositions which may contain bleaching agentsare described in the literature.

European patent application 30 096, for example, describes non-aqueousliquid detergents of liquid nonionic surfactants which may contain 20 to70% by weight of builders and 1 to 20% by weight of bleaching agents insuspended form. If desired, these detergents may contain anionicsurfactants, such as alkyl benzene sulfonates, olefin sulfonates, alkylsulfates or soap, optical brighteners, dyes, fragrances or enzymes.

EP-B-0 460 810 describes a non-aqueous liquid dishwashing detergentwhich contains a non-aqueous organic carrier liquid and at least onecomponent selected from organic cleaning agents, builders, foaminhibitors and mixtures thereof and one component selected from anon-abrasive quantity of 0.5 to 10% of small substantiallywater-insoluble particles of silicon dioxide, aluminium oxide ortitanium oxide or mixtures thereof as anti-film forming agents. Thedescribed detergent may also contain 3 to 15% by weight of bleachingagent.

WO 94/01524 describes a substantially non-aqueous liquid detergentwhich, besides nonionic surfactant, contains up to 60% by weight ofbuilder and between 5 and 35% by weight of bleaching agent. The liquiddetergent composition described in this document additionally contains apolymer compound which reduces the viscosity of the dispersion of thesolid builders and bleaching agents in the nonionic surfactant in orderto obtain a free-flowing and pourable composition.

German patent application 36 26 572 describes a liquid detergentcontaining a builder, more particularly polyacetal carboxylate, ananti-geling agent and an anti-sedimentation agent dispersed in a liquidnonionic surfactant.

Storable bleach-containing liquid detergents can only be obtained whenthe bleaching agent is present in the form of a stable dispersion.Commercially available liquid detergents known from the documents citedabove have the disadvantage that further auxiliaries are required toobtain a stable dispersion. Since the dispersion present in commercialliquid detergents is limited in its stability, bleaching agents andenzymes cannot be incorporated alongside one another in these productsbecause the enzymes are destroyed by the bleaching agent.

Another problem known from the prior art is that liquid detergents tendto gel, particularly when they are stored at low temperatures or areused at low washing temperatures. The effect of gelation is that theliquid detergents show poor solubility so that, on the one hand, theirwashing power is affected and, on the other hand, the detergent cannotbe completely emptied from the dispensing compartment or a typicaldispensing aid while the washing machine is in operation. The gel isvery difficult to redisperse in the detergent composition. In addition,gelation leads to a distinct increase in viscosity which in turn affectsthe dispensing behavior of the liquid detergent. On the other hand, theviscosity of the liquid detergent should not be too low in order toprevent sedimentation of its solid constituents.

DESCRIPTION OF THE INVENTION

The production of bleach-containing liquid washing or cleaningformulations represents another difficulty. In general, stabledispersions of solid particles in the liquid phase are only obtainedwhen the solid particles have a small particle size and a narrowparticle size distribution. In view of the different productionprocesses involved, the particle sizes of the builder particles and thebleach particles are very different which leads to a very broad particlesize distribution. Large-diameter solid particles in particular lead tounstable dispersions.

The problem addressed by the present invention was to provide a stablebleach-containing liquid washing and cleaning formulation which wouldcontain the solid bleaching agents in the form of a stable dispersion,even when stored for prolonged periods, without any adverse effect onthe activity of the substances present therein and which could alsocontain components sensitive to bleaching agents. Another problemaddressed by the present invention was to provide a process for theproduction of such formulations.

Accordingly, the present invention relates to a non-aqueous liquid orwashing or cleaning formulation which contains more than 20 to less than78% by weight of nonionic surfactants, 0.1 to 25% by weight of anionicsurfactants, 1 to less than 20% by weight of water-soluble builders andmore than 20 to 35% by weight of bleaching agents.

It has surprisingly been found that the formulation according to theinvention contains a special combination of washing- or cleaning-activecomponents so that the invention a provides a free-flowing, storableliquid washing and cleaning formulation which consists almostexclusively of active substance. Tests have shown that, by using solublebuilders, the traces of water introduced through the raw materials canbe bound so that the bleaching system and also the enzymes and/orsoil-repelling polymers, if any, can be stabilized. The anionicsurfactants present in accordance with the invention can also contributetowards better dispersion of the bleaching agents. It has been foundthat, in particular, the fatty alkyl sulfate added in accordance withthe invention and/or the fatty acid soap ensure that a stable matrix canbe built up for the dispersion of the bleaching system. In contrast tothe polymers described in the prior art, which are used as stabilizersfor the bleaching system, the fatty acid monoesters and/or soaps usedcontribute towards the washing performance of the formulation.

It has also been found that the soluble builders can reduce theabove-described gelation often observed in liquid or washing or cleaningformulations and can reduce the yield point and the zero shearviscosity. This improves the solubility of the formulation according tothe invention which leads to an overall improvement in its washing orcleaning performance. It has also been found that soluble builderscontribute less than insoluble zeolites or phosphates towards increasingthe viscosity of the washing or cleaning formulation so that largerquantities of solid bleaching agent can be incorporated. On the otherhand, the zero shear viscosity of the formulations according to theinvention is still high enough to prevent sedimentation of the solidparticles.

The present invention also relates to a process for the production of anon-aqueous liquid washing or cleaning formulation containing more than20 to less than 78% by weight of nonionic surfactants, 0.1 to 25% byweight of anionic surfactants, 1 to less than 20% by weight ofwater-soluble builder and more than 20 to 35% by weight of bleachingagents, characterized in that the solids present or partial amountsthereof are premixed with the nonionic surfactants or partial amountsthereof and ground in such a way that the temperature of the mixturedoes not exceed 45° C.

It has surprisingly been found that, in the practical application of theprocess according to the invention, the solid particles to be used, suchas builder and bleaching agent, may be used in virtually any particlesize distribution and that the mixture can be obtained in the form of astable dispersion after grinding. In order to minimize the exposure ofthe components to heat, the temperature of the mixture should not exceed35° C.

The expression "non-aqueous" in the context of the invention means thatthe formulation preferably does not contain any free water which is notbound as water of crystallization or in comparable form in order toprevent decomposition of the peroxide bleaching agent. In some cases,small quantities of free water, more particularly quantities of up to 5%by weight, are tolerable, in which case the ratio of bleaching agent tofree water should be at least 3:1.

The formulation according to the invention contains more than 20% byweight to less than 78% by weight and preferably 30% by weight to 60% byweight of nonionic surfactants. Preferred nonionic surfactants arealkoxylated, more particularly ethoxylated or ethoxylated andpropoxylated, fatty acid alkyl esters, preferably containing 1 to 4carbon atoms in the alkyl chain, more particularly the fatty acid methylesters which are described, for example, in Japanese patent applicationJP 58/217598 or which are preferably produced by the process describedin International patent application WO-A-90/13533.

Other suitable nonionic surfactants are liquid, alkoxylated, preferablyethoxylated, alcohols, more especially primary alcohols, preferablycontaining 8 to 18 carbon atoms (alkyl polyglycol ethers) and an averageof 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which thealcohol radical may be linear or 2-methyl-branched or may contain linearand methyl-branched radicals in the form of the mixtures typicallypresent in oxoalcohol radicals. However, particularly preferred nonionicsurfactants of this type are alcohol ethoxylates containing linearradicals of alcohols of native origin with 8 to 18 carbon atoms, forexample coconut fatty alcohol, tallow fatty alcohol or oleyl alcohol,which may contain on average 2 to 8 EO units per molecule. Preferredethoxylated alcohols include, for example, C₁₂₋₁₄ alcohols containing 3EO units or 7 EO units, C₉₋₁₁ alcohols containing 3 EO units, 5 EO unitsor 7 EO units, C₁₁₋₁₅ alcohols containing 5 EO units or 7 EO units andmixtures thereof, such as mixtures of C₁₂₋₁₄ alcohol containing 3 EOunits and C₁₂₋₁₈ alcohol containing 5 EO units. The degrees ofethoxylation mentioned are statistical mean values which may be a wholenumber or a broken number for a particular product. Preferred alcoholalkoxylates have a narrow homolog distribution (narrow rangeethoxylates, NRE).

The formulation according to the invention may contain alkylpolyglycosides, fatty acid alkyl esters or polyhydroxyfatty acid amidesas further nonionic surfactants.

In addition, the formulation according to the invention contains 0.5 to25% by weight, preferably 1 to 15% by weight and more preferably 4 to12% by weight of anionic surfactants. C₆₋₂₂ alkyl sulfates, C₈₋₁₈ alkanesulfonates, alkyl benzene sulfonates and/or fatty acid soaps arepreferably used. Suitable alkyl sulfates are, in particular, thesulfuric acid monoesters of C₆₋₁₈ fatty alcohols, such as octyl, lauryl,myristyl, cetyl or stearyl alcohol, or the fatty alcohol mixturesobtained from coconut oil, palm oil and palm kernel oil which mayadditionally contain unsaturated alcohols, for example oleyl alcohol.

Preferred surfactants of the sulfonate type are C₉₋₁₃ alkyl benzenesulfonates, C₈₋₁₈ alkane sulfonates, olefin sulfonates, i.e. mixtures ofalkene and hydroxyalkane sulfonates, and disulfonates which areobtained, for example, from C₁₂₋₁₈ alkanes or C₁₂₋₁₈ monoolefins with aterminal or internal double bond by sulfonation with gaseous sulfurtrioxide and subsequent alkaline or acidic hydrolysis of the sulfonationproducts.

Suitable soaps, which are included among the anionic surfactants in thecontext of the present invention, are in particular saturated fatty acidsoaps, the salts of lauric acid, myristic acid, palmitic acid or stearicacid and soap mixtures derived in particular from natural fatty acids,for example caproic acid, caprylic acid, cocofatty acid, palm kernelfatty acid or tallow fatty acid.

The formulation according to the invention may contain C₆₋₁₈ alkylpolyglycol ether sulfonates, glycerol ether sulfonates, glycerol ethersulfates, hydroxy mixed ether sulfates, monoglyceride sulfates,sulfosuccinates, sulfotriglycerides, amido acids, C₆₋₁₈ fatty acid amideether sulfates, C₆₋₁₈ alkyl carboxylates, fatty acid isethionates,N-C₆₋₁₆ -acyl sarcosinates, N-C₆₋₁₈ -acyl taurides, C₆₋₁₈ alkyloligoglycoside sulfates, C₆₋₁₈ alkyl phosphates and mixtures thereof asfurther anionic surfactants.

Sulfuric acid monoesters and the soaps may be present in the formulationaccording to the invention either individually or in the form ofmixtures, for example in a total quantity of 1 to 15% by weight and,more particularly, 1 to 10% by weight.

In one preferred embodiment, the formulation according to the inventiondoes not contain any other anionic surfactants than the soaps.

In addition, the formulation according to the invention contains 1 toless than 20% by weight and preferably 8 to less than 20% by weight ofwater-soluble builders. Suitable builders are any water-soluble organicand inorganic builders. Useful organic builders are, for example, mono-and/or polycarboxylates, preferably the polycarboxylic acids used in theform of their sodium salts, such as citric acid, adipic acid, succinicacid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids,nitrilotriacetic acid (NTA), providing its use is not objectionable onecological grounds, and mixtures thereof. Particularly preferred saltsare the salts of polycarboxylic acids, such as citric acid, adipic acid,succinic acid, glutaric acid, tartaric acid, sugar acids and mixturesthereof, sodium citrate being particularly preferred. Suitable inorganicbuilders are, in particular, crystalline layer-form sodium silicatescorresponding to general formula (I) NaMSi_(x) O_(2x+1).yH₂ O, in whichM is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number of0 to 20, preferred values for x being 2, 3 or 4. Correspondingcrystalline layer silicates are described, for example, in Europeanpatent application 164 514. Preferred crystalline layer silicatescorresponding to formula (I) are those in which M is sodium and xassumes a value of 2 or 3. Both β- and δ-sodium disilicates Na₂ Si₂O₅.yH₂ O are particularly preferred.

In addition, layer silicates of natural and synthetic origin may beused. Layer silicates such as these are known, for example, from patentapplications DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405. Theirsuitability is not confined to a particular composition or structuralformula. However, smectites, especially bentonites, are preferred.

Other suitable builders are, for example, amorphous silicates with a lowwater content, preferably with a water content below 15% by weight, andsilicates in the form of compounds, for example soda/silicate compounds.

In one preferred embodiment, the formulation according to the inventioncontains as builder a mixture of mono- and/or polycarboxylates andcrystalline layer-form sodium silicates corresponding to general formula(I) NaMSi_(x) O_(2x+1).yH₂ O, in which M is sodium or hydrogen, x is anumber of 1.9 to 4 and y is a number of 0 to 20, preferred values for xbeing 2, 3 or 4, and/or amorphous silicates. The mono- and/orpolycarboxylates and the crystalline layer silicates are present in aratio of preferably 4:1 to 1:4, more preferably 3:1 to 1:3 and mostpreferably 1.2:1 to 1:1.2.

The formulation according to the invention contains bleaching agents ina quantity of more than 20 to 35% by weight and preferably in a quantityof more than 20 to 30% by weight. Among the compounds yielding H₂ O₂ inwater which are used as bleaching agents, the sodium borates,particularly sodium perborate tetrahydrate and sodium perboratemonohydrate, are particularly important. Other suitable bleaching agentsare, for example, sodium percarbonate, peroxypyrophosphates, citrateperhydrates and H₂ O₂ -yielding peracidic salts or peracids, such asperbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioicacid.

To ensure stable dispersion of the solids in the formulation accordingto the invention, the solids present, for example the builders and thebleaching agent, preferably have such a particle size distribution thatat least 90% of the particles are smaller than 15 μm and, in particular,smaller than 10 μm and at most 75% and, in particular, 70% of theparticles are smaller than 5 μm.

In order to obtain an improved bleaching effect where washing is carriedout at temperatures of 60° C. or lower, bleach activators may beincorporated in the formulations according to the invention. Examples ofbleach activators are the N-acyl or O-acyl compounds which form organicperacids with H₂ O₂, preferably N,N'-tetraacylated diamines, alsocarboxylic anhydrides and esters of polyols, such as glucosepentaacetate. The content of bleach activators in the bleach-containingformulations is in the usual range, preferably from 1 to 10% by weightand more preferably from 3 to 8% byweight. Particularly preferred bleachactivators are N,N,N',N'-tetraacetyl ethylenediamine (TAED) and1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DAHT).

In one preferred embodiment, the formulation according to the inventioncontains enzymes. The enzyme content of the formulation may be from 0.2to 4% by weight. Suitable enzymes are those from the class of proteases,lipases, amylases and cellulases or mixtures thereof. Particularlysuitable enzymes are the enzymes obtained from bacterial strains orfungi, such as Bacillus subtilis, Bacillus licheniformis andStreptomyces griseus. The enzymes may be adsorbed to supports and/orencapsulated in shell-forming substances in known manner.

The formulation according to the invention may additionally containstabilizers for the enzymes. The stabilizers used, which are alsosuitable as stabilizers for per compounds, may be selected from thesalts of polyphosphonic acids, more especially1-hydroxyethane-1,1-diphosphonic acid (HEDP). The polyphosphonic acidsmentioned above are also suitable for binding traces of heavy metal.Suitable heavy metal complexing agents are, for example, the HEDPmentioned above and ethylenetriamine pentamethylene phosphonic acid(DTPMP).

The formulation according to the invention may additionally containsoil-releasing polymers. The soil-releasing polymers are present inquantities of preferably 0.01 to 5% by weight and, more preferably,0.05% by weight to around 3% by weight. Suitable soil-releasing polymersare, for example, polyethylene oxides having a molecular weight of 3,000to 600,000.

Preferred soil-releasing polymers are polymers containing ethyleneglycol terephthalate groups and polyethylene glycol terephthalate groupswhich each comprise 17 to 110 ethylene glycol groups, the molar ratio ofethylene glycol terephthalate to polyethylene glycol terephthalate inthe polymer being 50:50 to 90:10. In these compounds, the molecularweight of the linking polyethylene glycol units is in the range from 750to 5,000. The polymers may have an average molecular weight of around5,000 to around 200,000. The ethylene glycol terephthalate andpolyethylene glycol terephthalate may be arbitrarily distributed in thepolymer.

Preferred polymers are those with molar ratios of ethylene glycolterephthalate to polyethylene glycol terephthalate of 65:35 to 90:10 andpreferably 65:35 to 80:20, the linking polyethylene glycol units havinga molecular weight of 750 to 5,000 and preferably 1,000 to 3,000 and thepolymer having a molecular weight of 10,000 to 50,000. One example ofcommercial polymers of this type is the product marketed under the nameof "Repel-O-Tex SRP3" by Rhone-Poulenc, France.

The soil-releasing polymers preferably, used may be prepared by knownpolymerization processes, the starting materials being used in thequantities required to obtain the ratios of ethylene glycolterephthalate to polyethylene glycol terephthalate mentioned above. Forexample, the process described in U.S. Pat. No. 3,479,212 may be used toproduce suitable polymers.

In addition to the builders mentioned above, the formulations accordingto the invention may contain other inorganic substances. Alkali metalcarbonates, for example soda, alkali metal hydrogen carbonates, alkalimetal sulfates and phosphates are mentioned as suitable substances inthis regard. This additional inorganic material may be present inquantities of up to 10% by weight.

The formulations according to the invention may contain opticalbrighteners and redeposition inhibitors, foam inhibitors and also dyesand perfumes are further constituents.

The formulations according to the invention preferably have a zero shearviscosity h_(o) at 20° C. of 100 to 10,000 Pas and preferably 500 to6,000 Pas and a pseudoplastic flow behavior h on application of 100 to10,000 mPas and preferably 500 to 4,000 mPas at a shear rate D of 30/s.The yield point t_(F) at 20° C. is 0.5 to 10 Pa and preferably 1 to 5Pa.

The formulation according to the invention preferably contains nosolvent. In one particularly preferred embodiment, the formulationaccording to the invention has an active substance content of 100%.

The formulation according to the invention has a pH value of preferably7 to 11 and more preferably 8.5 to 10.5.

The formulations according to the invention may be used both indetergents and in cleaning products. For example, high-viscosityformulations according to the invention may be used in the commercialcleaning of textiles.

Production process

In the process according to the invention, the solids present or partialamounts thereof are premixed with the nonionic surfactants or partialamounts thereof and ground in such a way that the temperature of themixture does not exceed 45° C., preferably 40° C. and, more preferably,35° C. "Partial amount" in the context of this description means part ofthe total quantity of solids or the total quantity of nonionic liquidsurfactants and can also mean the total quantity of an individualcomponent, for example builder or bleaching agent, as part of the totalsolids or nonionic liquid surfactants. The ground partial amounts andother components, if any, may then be mixed to form the requiredformulation. In a preferred embodiment, the solid particles of thenon-aqueous liquid formulation produced in accordance with the inventionhave such a particle size distribution that at least 90% of theparticles are smaller than 10 μm and at most 70% of the particles aresmaller than 5 μm.

In one embodiment, all the components of the formulation according tothe invention are premixed to form a mill batch and are then ground tothe required particle size distribution in a single pass through a mill.A procedure such as this is particularly advantageous when the solidparticles are smaller than 1.0 mm and preferably smaller than 0.8 mm.

If the solids contain particles with a very broad particle sizedistribution or rather with particles sizes of larger than 1.0 mm, forexample enzymes in granular form, the mill batch may either be passedthrough the same mill several times (discontinuous grinding) or themixture may be ground to the necessary fineness by multistage grindinginvolving continuous passage through mills arranged in tandem. In thecase of discontinuous grinding, three-pass grinding and, moreparticularly, two-pass grinding is preferred. In the case of continuousmultistage grinding, three and preferably two mills are arranged intandem.

In both the discontinuous procedure and the continuous procedure, themixture may be preground in a first grinding step, i.e. in the firstpass or in the first stage, to such a particle size that around 90% ofthe particles are smaller than 100 μm and preferably smaller than 50 μm.The particles may then be ground to the required particle sizedistribution in one or more additional grinding stages.

In another embodiment of the process according to the invention, thesolid particles without enzymes are premixed with a partial amount ofthe liquid nonionic surfactants while the enzymes are premixed withanother partial amount of the liquid nonionic surfactants and separatelyground by so-called partial-stream grinding. The mill batches are thenmixed to form the required formulation, optionally with other componentswhich have not been ground.

For incorporation in the liquid detergent according to the invention,the enzymes may be used in the form of granules and, more particularly,in the form of a liquid enzyme preparation.

When the individual components of the formulation according to theinvention are premixed, a viscous dispersion is obtained. Shear forcesinter alia are generated in the grinding of viscous dispersions,increasing the energy density in the dispersion and leading to heating.The heat generated is greater, the stronger the shear forces. Themagnitude of the shear forces generated is determined inter alia by thesize of the grinding chamber and the level to which it is filled.Heating of the material being ground can be avoided by directlydissipating the heat generated and/or by minimizing the shear forces.

The heat of friction generated can be dissipated in known manner. In oneembodiment, the grinding chamber is defined by large cooling surfaces towhich the heat generated is given off. The grinding chamber ispreferably surrounded by a cooling medium so that the heat generated isgiven off to the surface of the grinding chamber and is transferred fromthere to a cooling medium. The transfer of heat is more effective, thehigher the thermal conductivity of the material with which the surfaceof the grinding chamber is lined or the larger the surface of thegrinding chamber.

The temperature of the cooling medium generally depends upon the thermalconductivity of the material with which the grinding chamber is lined.The higher the thermal conductivity of the constituent material of thegrinding chamber, the higher the temperature of the cooling medium canbe. It is important to ensure that the temperature of the cooling mediumis not too low. The suspension according to the invention normally has asolidus point of 0° to 15° C. If the temperature of the cooling mediumis low, the wall of the grinding chamber is in danger of becoming toocold so that the temperature of the mixture to be ground is locallybelow the melting point on the surface of the wall of the grindingchamber. This still viscous to solid substance can remain there and forma boundary layer which can impede the dissipation of heat and can leadto unsatisfactory grinding. In addition, the material forming thisboundary layer is no longer effectively involved in the grindingprocess.

In one preferred embodiment, the size of the grinding chamber, theextent to which it is filled with grinding balls, the constituentmaterial of the walls of the grinding chamber and also the nature andtemperature of the cooling medium are adapted to one another in such away that the composition to be ground is reduced to the requiredparticle size distribution in an economically acceptable time or ratherat a high throughput without the temperature of the dispersion exceeding45° C., preferably 40° C. and more preferably 35° C.

The mixture is preferably ground in wet ball mills or roll mills.Stirred ball mills and ring ball mills with a narrow grinding chamberand a large cooling surface are particularly preferred.

The ratio of the drive energy acting on the grinding rotor in thesemills to the throughput of mixture to be ground should be greater than0.001 kWh/kg and is preferably greater than 0.05 kWh/kg and morepreferably greater than 0.125 kWh/kg.

The surfaces of those parts of the mills which come into contact withthe product should be harder by a reasonable margin than the substancesto be ground. Accordingly, suitable materials are, for example, whitecast iron, steel, hardened steel and hardened stainless steel. Inaddition, the various parts of the mill may be coated with hard metalsor ceramics such as, for example, aluminium oxide or silicon carbideceramics.

EXAMPLES

Production of the formulations according to the invention:

The anionic surfactant was dissolved in the nonionic surfactants at 90°C. and then cooled to room temperature. The builders and the bleachingagent and any other components present were then successively added.

The product was then wet-round in a cooled ball mill (zirconium oxideballs, diameter 1.2 to 1.6 mm, maximum temperature ≦35° C.).

The formulations are set out in Table 1 (a and b), the quantities of theindividual components being shown in % by weight.

                  TABLE 1a    ______________________________________                Example    ______________________________________                  1      2      3    4    5    6    Dehydol ® LT7.sup.1)                  --     6.5    11.3 27.0 6.3  9.0    Dehydol ® LST 80/20.sup.2)                  19.2   17.0   20.0 21.1 17.0 19.0    Lutensol ® AO7.sup.3)                  24.6   14.0   --   --   14.0 16.9    Maranil ® A.sup.4)                  5.4    7.8    7.1  4.0  7.8  7.8    Sulfopon ® T.sup.5)                  1.4    --     1.4  --   --   --    Edenor ® HT 35.sup.6)                  --     0.1    --   0.4  --   --    Na Citrate    15.0   13.0   9.0  16.0 13.0 --    SKS-6.sup.7)  --     4.0    8.0  --   4.0  13.0    Peroborate monohydrate                  21.0   21.0   25.0 21.0 21.0 21.0    TAED          6.0    6.0    7.0  7.3  6.0  6.0    Triacetin     4.7    4.7    4.7  --   4.7  4.7    Soda          --     4.0    4.0  --   4.0  --    VP1132.sup.8) 0.2    0.2    0.2  0.2  0.2  0.2    Turpinal ® 2 NZ.sup.9)                  0.6    --     0.6  0.6  --   --    BLAP ® 200.sup.10)                  1.7    1.7    1.7  1.7  1.7  2.1    Water         0.2    --     --   0.7  0.3  0.3    ______________________________________

                  TABLE 1b    ______________________________________                  Examples                  7        8      9    ______________________________________    Dehydol 04.sup.11)                    --         --     15.0    Dehydol 980.sup.12)                    --         14.2   16.3    Dehydol LS 6.sup.13)                    26.0       25.0   14.0    APG/soda compound.sup.14)                    8.0        8.0    --    Lutensol AO7    13.0       --     --    Maranil A       4.5        --     --    Octyl Sulfate   5.0        7.0    7.0    C.sub.18-14 fatty acid                    1.0        1.0    1.0    Na Citrate      15.0       7.0    15.0    Sokalan DCS.sup.15)                    --         10.0   --    Perborate monohydrate                    21.0       21.0   21.0    TAED            6.0        6.0    6.0    Soda            --         --     4.0    Polyethylene oxide                    0.1        0.1    0.1    Molecular weight 600.000    Water           0.4        0.7    0.6    ______________________________________     .sup.1) Dehydol ® LT 7 is an ethoxylated C.sub.12-18 fatty alcohol     containing an average of 7 EO units (a product of Henkel KGaA, Dusseldorf     .sup.2) Dehydol ® LST 80/20 is a mixture of 80% of an ethoxylated     C12-18 fatty alcohol containing an average of 5 EO units and 20% of an     ethoxylated C.sub.12-14 fatty alcohol containing an average of 3 EO units     (a product of Henkel KGaA, Dusseldorf)     .sup.3) Lutensol ® AO7 is an ethoxylated C.sub.12-15 oxofatty alcohol     containing an average of 7 EO units (a product of BASF, Ludwigshafen)     .sup.4) Maranil ® A is a C.sub.11-13 alkyl benzene sulfonate (a     product of Huls AG, Marl)     .sup.5) Sulfopon ® T is a C.sub.16-18 fatty alcohol sulfate (a produc     of Henkel KGaA, Dusseldorf)     .sup.6) Edenor ® HT 35 is a C.sub.16-18 fatty acid soap (a product of     Henkel KGaA Dusseldorf)     .sup.7) SKS6 is a crystalline layer silicate (a product of Hoechst AG,     Frankfurt)     .sup.8) VP 1132 is a silicone oil (a product of Dow Corning)     .sup.9) Turpinal ®2 NZ is a hydroxy ethyl diphosphonate (a product of     Henkel KGaA, Dusseldorf)     .sup.10) BLAP ® 140 is a protease (a product of Henkel KGaA,     Dusseldorf)     .sup.11) C.sub.8 fatty alcohol + 4 moles EO (Henkel KGaA)     .sup.12) C.sub.10-14 fatty alcohol + 1 mole PO + 6 moles EO (Henkel KGaA)     .sup.13) C.sub.12-14 fatty alcohol + 6 moles EO (Henkel KGaA)     .sup.14) C.sub.12-14 alkyl polyglucoside:soda granules (ratio by weight     1:1)     .sup.15) Mixture of adipic acid, glutaric acid and succinic acid (BASF).

Examples 7 to 9 are suitable both for washing textiles and, inparticular, for cleaning hard surfaces.

The rheological data of formulation No. 3 were determined with aRheometrics RFSII shear-rate-controlled rotational rheometer. Theresults are set out in Table 2.

The stability of formulations 5 and 6 in storage was tested at roomtemperature and at 30° C. The results are set out in Table 3.

                  TABLE 2    ______________________________________    Temperature    10° C.                              20° C.                                      30° C.    ______________________________________    Yield point (Pa)                   2.8        2.0     2.0    Zero shear viscosity                   5900       3800    3000 (Pas)    Viscosity D = 30/s (Pas)                   5.0        3.0     2.2    ______________________________________

It can be seen from Table 2 that formulation No. 3 according to theinvention shows very good flow properties, the zero shear viscositystill being high enough to prevent the solid particles from sedimenting.

                  TABLE 3    ______________________________________                    Example                    5     6    ______________________________________    Viscosity (Pas)   141     365    AO.sup.1 (%)      3.10    3.10    Stability in    storage at room temperature    1 week   AO.sup.1 (%) 3.04    3.10             intact (%)   98.1    100.0    8 weeks  AO.sup.1 (%) 2.84    2.94             intact (%)   91.6    94.8    Stability in storage at 30° C.    1 week   AO.sup.1 (%) 3.07    3.10             intact (%)   99.0    100.00    8 weeks  AO.sup.1 (%) 2.88    2.97             intact (%)   92.9    95.8    ______________________________________     .sup.1 Active oxygen

Table 3 shows the high stability in storage of formulations 5 and 6according to the invention over a long period both at room temperatureand at elevated temperature.

We claim:
 1. A substantially non-aqueous, free-flowing, storable liquidwashing or cleaning formulation comprising:A) from more than 20 to lessthan 78% by weight of at least one nonionic surfactant; B) from 0.1 to4% by weight of at least one anionic surfactant selected from the groupconsisting of a C₆₋₂₂ alkyl sulfate, a C₈₋₁₈ alkane sulfonate, an alkylbenzene sulfonate and a fatty acid soap; C) from 1 to less than 20% byweight of at least one water-soluble builder; and D) from more than 20to 35% by weight of at least one bleaching agent.
 2. The formulation ofclaim 1 wherein component A) is present in from about 30 to about 60% byweight.
 3. The formulation of claim 2 wherein component C) is present infrom about 8 to less than 20% by weight.
 4. The formulation of claim 3wherein component D) is present in from more than 20 to about 30% byweight.
 5. The formulation of claim 1 wherein component A) is at leastone of an alkoxylated fatty acid alkyl ester, an alkoxylated alcohol, analkyl polyglycoside, a fatty acid alkyl ester or a polyhydroxy-fattyacid amide.
 6. The formulation of claim 1 wherein component B) consistsof a fatty acid soap.
 7. The formulation of claim 1 wherein component C)is at least one mono- or polycarboxylate.
 8. The formulation of claim 7wherein component C) is a salt of a polycarboxylic acid.
 9. Theformulation of claim 7 wherein component C) also contains at least oneof a crystalline layer-form sodium silicate corresponding to the formulaNaMSi_(x) O_(2x+1).yH₂ O, in which M is sodium or hydrogen, x is anumber of 1.9 to 4 and y is a number of 0 to 20, or an amorphoussilicate.
 10. The formulation of claim 1 wherein component D) is a saltof a peracid.
 11. The formulation of claim 10 wherein the salt of aperacid is sodium perborate.
 12. The formulation of claim 1 whereincomponent D) is present in the form of a stable dispersion in which atleast 90% of the dispersed particles are smaller than 15 μm.
 13. Theformulation of claim 12 wherein not more than 75% of the dispersedparticles are smaller than 5 μm.
 14. The formulation of claim 1 whereinthe formulation also contains at least one of a bleach activator, anenzyme, or a soil-releasing polymer.
 15. A process for the preparationof the formulation of claim 1 comprising the steps ofI) mixing togetherat least part of the solid components of the formulation with at leastpart of component A); II) grinding the resulting mixture whilemaintaining the temperature thereof at 45° C. or less; and III) mixingthe resulting ground mixture with the remaining components of theformulation.
 16. The process of claim 15 wherein the temperature in stepII) does not exceed 35° C.
 17. The process of claim 15 wherein step II)is carried out by passing said resulting mixture through a wet ball millor a roll mill at least once.
 18. The process of claim 17 wherein thewet ball mill is used which is a stirred ball mill with a narrowgrinding chamber and a large cooling surface.
 19. A process for thepreparation of the formulation of claim 1 wherein the formulation alsocontains at least one enzyme comprising the steps ofI) premixing the atleast one enzyme with part of component A); II) mixing together thesolid components of the formulation with the remaining part of componentA); III) separately grinding the mixtures from steps I) and II) whilemaintaining the temperature of each mixture at 45° C. or less; and IV)combining said separately ground mixtures together with the remainingcomponents of the formulation; wherein steps I) and II) can be carriedout in reverse order.